Catalyst for preparing chlorine by oxidation of hydrogen chloride and preparation thereof

ABSTRACT

The present invention relates to a catalyst for producing chlorine by oxidation of hydrogen chloride and a method for preparing the same. The catalyst comprises a support and active ingredients that comprise 1-20 wt % of copper, 0.01-5 wt % of boron, 0.1-10 wt % of alkali metal element(s), 0.1-15 wt % of one or more rare earth elements, and 0-10 wt % of one or more elements selected from magnesium, calcium, barium, manganese, iron, nickel, cobalt, zinc, ruthenium or titanium based on the total weight of the catalyst. The catalyst is prepared by a two-step impregnation method. Comparing with the available catalysts of the same type, the catalyst according to the present invention has greatly improved conversion and stability.

FIELD OF THE INVENTION

The present invention relates to a catalyst for preparing chlorine bythe oxidation of hydrogen chloride and a method for producing the same.

BACKGROUND OF THE INVENTION

Chlorine is an important basic chemical material which has been widelyused in the industries of novel materials such as polyurethanes,silicons, epoxy resins, chlorinated rubbers, chlorinated polymers,chlorinated hydrocarbons and the like; the new energy industries such asmanufacture of polycrystalline silicon and the like; the industries offine chemicals such as disinfectors, detergents, food additives,cosmetic additives and the like; the industries ofpesticides/pharmaceuticals such as synthetic glycerin, chlorobenzenes,chloroacetic acid, benzyl chloride, PCl₃ and the like; as well as theindustries of paper manufacture, textile industries, metallurgyindustries and petroleum and chemical industries, etc.

Almost all chlorine is produced by the electrolysis of sodium chloridesolution in the industries. This process has two big problems. The firstone is the high electricity consumption of up to 2760 kWh per tonchlorine, that makes the electricity consumption of the entirechlor-alkali industry comprises about 5% of the total industrialelectricity consumption in China. The second one is the processco-produces chlorine and sodium hydroxide. While when sodium hydroxiderequirements do not coincide with the demand for chlorine whichincreases greatly due to the rapid development of chlorine-consumingindustries, oversupply of sodium hydroxide occurs. Thus, it is necessaryto find a new source of chlorine for the further development ofchlorine-consuming industries.

On the other hand, since chlorine is used as a reaction medium in mostchlorine-consuming industries, it is not part of the final products butdischarged from reaction systems in a form of hydrogen chloride as aby-product. As the rapid development of chlorine-consuming industries,it is increasingly difficult to find outlets for hydrogen chloride. Theresulting by-produced hydrochloric acid has low added value, needs highcost for transport and storage and the sale is difficult. Also, 20-50times of waste water produced in subsequent applications generates agreat deal of pressure on the environment. In the case of co-productionof PVC, the domestic capacity of PVC is much excessive, and the exportamount, price and utilization of capacity are always unsatisfied. Thus,under the current conditions, the outlet of hydrogen chloride has becomea bottleneck restricting further development of the chlorine-consumingindustries.

If the by-produced hydrogen chloride could be directly transformed intochlorine, the closed circulation of “chlorine” would be realized,thereby the two bottlenecks of upstream and downstream of thechlorine-consuming industries can be essentially solved. The oxidationof hydrogen chloride by oxygen or air as an oxidant to prepare chlorineis a good route. This reaction is represented by the followingstoichiometric formula:

$ {{2{HCl}} + {\frac{1}{2}O_{2}}}rightarrow{{Cl}_{2} + {H_{2}O} - {57.7\mspace{14mu} {kJ}\text{/}{mol}}} $

Currently, there are three different routes to carry out this process,which are the catalytic oxidation method, the cyclic oxidation methodand the oxidative electrolysis method. Among them, the representativecyclic oxidation method is developed by Dupont. In this method, sulfuricacid is used as a cyclic oxidative medium and nitric acid is used as acatalyst. Thus, its equipment investment and operational cost are high,and its operation is complex and lack of flexibility. The oxidativeelectrolysis method can well relief the second problem, which wasdescribe above, in the chlor-alkali industry. However, it still has anelectricity consumption level of above 1700 kWh per ton chlorine, andthereby the status of high electricity-consumption in the production ofchlorine is not substantially improved. Furthermore, in comparison toion-membrane electrolysis, the method of oxidative electrolysis ofhydrochloric acid requires more complex equipments and has no advantagesin economical efficiency and operability. This technique is masteredonly by Bayer. However, Bayer introduced the catalytic oxidationtechnique from Sumitomo (Japan) while is actively finding a market forits oxidative electrolysis technique.

Objectively, the method of catalytic oxidation of hydrogen chloride alsorequires relatively large equipment investment, and in general, the costfor production of chlorine is estimated to be slightly higher than thatof the method of ion membrane electrolysis according to the presenttechnique of Sumitomo (Japan). The greatest advantage of this method isits low electricity consumption of only about 230 kWh per ton chlorine.In addition, it is an environment-friendly chemical process.

In the reported catalysts for hydrogen chloride oxidation, the activeingredients mainly are metal elements such as copper, chromium, gold andruthenium, etc. Among them, gold and ruthenium-based catalysts areexpensive and have poor performance in sulfur-tolerance. Chromium-basedcatalysts pollute the environment due to their higher toxicity. Thus,the above two kinds of catalysts have such problems of high economiccost or environmental pollution or the like in use. Compared with them,copper-based catalysts have both advantages of lower cost and beingenvironmentally friendly, thus are of great interests.

CN200710121298.1 discloses a catalyst containing cupric chloride,potassium chloride and cerium chloride with alumina as support andtreated by phosphoric acid. For this catalyst the yield of chlorine is80.1% under the conditions that the ratio of hydrogen chloride andoxygen is 1:1, the temperature of fixed bed reactor is 400° C., thereaction pressure is 0.1 MPa and the space velocity of hydrogen chlorideis 0.8 hr⁻¹. However, this catalyst has a relatively low activity, andthe loss of the cupric chloride ingredient under a higher temperatureimpairs the use life of the catalyst.

CN200910027312.0 discloses a catalyst containing cupric chloride,potassium chloride, manganese nitrate and cerium nitrate supported onsilica gel or ReY molecular sieve. With 25 g of this catalyst, thehydrogen chloride conversion is 83.6% with both of hydrogen chloride andoxygen flow rates of 200 ml/min at a reaction temperature of 380° C.However, this catalyst still has the disadvantages of loss of copperingredients and a relatively low space velocity.

U.S. Pat. No. 4,123,389 discloses a copper-based catalyst with silicagel, alumina or titania as a support, in which the loading amount ofactive ingredients is between 25% and 70%. The process of preparation ofthe catalyst needs organic solvents and thus causes great environmentalpollution.

Therefore, it is still a technical challenge in the related field todevelop a cheap, environment-friendly catalyst with high activity andstability for production of chlorine by catalytic oxidation of hydrogenchloride.

SUMMARY OF THE INVENTION

One object of the invention is to provide a catalyst for production ofchlorine by catalytic oxidation of hydrogen chloride which overcomes thedisadvantages of the current copper-based catalysts and the catalystherein has good reaction activity and stability.

Another object of the invention is to provide a method for preparing theabove catalyst for production of chlorine by catalytic oxidation ofhydrogen chloride.

The catalyst for production of chlorine by catalytic oxidation ofhydrogen chloride according to the present invention comprises a supportand active ingredients comprising 1-20 wt % of copper, 0.01-5 wt % ofboron, 0.1-10 wt % of alkali metal element(s), 0.1-15 wt % of one ormore rare earth elements, and 0-10 wt % of one or more elements selectedfrom magnesium, calcium, barium, manganese, iron, nickel, cobalt, zinc,ruthenium and titanium, the weight percent of each ingredient is basedon the total weight of the catalyst.

The method for preparing the catalyst according to the present inventioncomprises the steps of:

(1) preparing a solution by dissolving a copper-containing compound asrequired and optionally a compound containing a transition metal otherthan copper in water, then impregnating a support with the solution, anddrying the impregnated support;

(2) dissolving a boron-containing compound, a alkali metal-containingcompound, a rare earth metal-containing compound and a alkaline earthmetal-containing compound as required in water, then impregnating thedried solid obtained in step (1) with the solution, and drying theimpregnated solid;

(3) calcining the solid obtained in step (2) at a temperature of450-650° C. for 1-5 h to obtain the catalyst.

The catalyst according to the present invention can be easily prepared.Meanwhile, comparing with gold and ruthenium-based catalysts, thecatalyst according to the invention has a relatively lower price. Due tofree of the toxic ingredients such as Cr, etc., the catalyst isrelatively environment-friendly and does not cause secondary pollution.Comparing with the available copper-containing catalysts, the catalystaccording to the invention has a better stability due to the addition ofboron which greatly inhibits the loss of the copper ingredient. Inaddition, in the two-step impregnation process, the copper-containingcompound and the compound containing a transition metal other thancopper are firstly loaded on the support by impregnation, and then theother ingredients are loaded on the support by the second impregnation,which makes the resulted catalyst has higher activity, and thereby ahigher yield of chlorine can be realized under a higher space velocityof hydrogen chloride. Comparing with the available copper-basedcatalyst, the catalyst provided by the present invention can improve theyield of chlorine by about 1%-3%, and even by about 4%-5%.

DETAILED DESCRIPTION OF THE INVENTION

The catalyst for oxidation of hydrogen chloride and the preparationmethod of the catalyst according to the invention are illustrated indetail below, however the present invention is not limited by thefollowing description in any way. In the present invention, the totalweight of the catalyst refers to the weight of the final catalystproduct.

According to the catalyst for oxidation of hydrogen chloride provided inthe present invention, preferably the catalyst comprises the followingactive ingredients: 4-15 wt %, more preferably 5-12 wt % of copper;0.1-4 wt %, more preferably 0.15-3 wt % of boron; 2-7 wt %, morepreferably 2.5-6 wt % of alkali metal element(s); 1-11 wt %, morepreferably 2-9 wt % of one or more rare earth elements; 1-8wt %, morepreferably 2-6 wt % of one or more elements selected from magnesium,calcium, barium, manganese, iron, nickel, cobalt, zinc, ruthenium andtitanium; as well as 60-90 wt %, preferably 60-85 wt % of a support.

In the catalyst according to the invention, the alkali metal element isany one selected from lithium, sodium, potassium and cesium, preferablyis sodium or potassium. The rare earth element is at least one selectedfrom lanthanide elements, preferably is one or more selected fromcerium, lanthanum, praseodymium and neodymium.

The support according to the invention is at least one selected frommolecular sieve, kaolin, diatomite, silica, alumina, titania andzirconia, preferably is molecular sieve or kaolin, and more preferablyis type Y molecular sieve (Y-zeolite).

According to the preparation method of the catalyst for oxidation ofhydrogen chloride of the invention, in steps (1) and (2), theimpregnation time preferably lasts 8-16 h and then dried at atemperature of 70-110 ° C. for 12-24 h.

In the process for preparation of the catalyst, the usedcopper-containing compound is a soluble salt of copper, preferably oneor more selected from cupric nitrate, cupric chloride and cupricacetate. In general, when two or more soluble copper salts are used,they can be combined in any proportions. More preferably, the usedcopper-containing compounds are cupric nitrate and cupric chloride.

The compound containing a transition metal other than copper is selectedfrom soluble salts of manganese, iron, nickel, cobalt, zinc, rutheniumand titanium, preferably one or more selected from correspondingnitrates, chlorides and acetates of manganese, iron, nickel, cobalt,zinc and titanium, and more preferably one or more of correspondingnitrates, chlorides and acetates of manganese, iron, cobalt and zinc.

The boron-containing compound is one or two or three of boric acid,sodium borate and potassium borate. The alkali metal compound is one ormore selected from chlorides, nitrates, acetates, carbonates and boratesof lithium, sodium, potassium, preferably one or more selected fromchloride, nitrate, acetate, carbonate and borate of sodium or potassium.The alkaline earth metal compound is one or more selected fromchlorides, nitrates, acetates, carbonates and borates of magnesium,calcium and barium, and preferably one or more selected from chlorides,nitrates, acetates, carbonates and borates of magnesium and calcium. Therare earth metal compound is one or more selected from nitrates andchlorides of cerium, lanthanum, praseodymium and neodymium, preferablyone or more selected from the nitrates.

The catalyst of the invention is useful in the reaction for producingchlorine by catalytic oxidation of hydrogen chloride, which may becarried out in a fixed bed reactor or in other reactors suitable forsuch reactions.

The reaction conditions for producing chlorine by the oxidation ofhydrogen chloride are that: the reaction temperature is 320-460° C.,preferably 360-400° C.; the reaction pressure is 0.1-0.6 MPa, preferably0.1-0.35 MPa; the mole ratio between hydrogen chloride and oxygen is0.5-9:1, preferably 1-4:1; and the mass space velocity of hydrogenchloride is 0.1-2.5 h⁻¹, preferably 0.5-2⁻¹.

The present invention provides the catalyst for producing chlorine bythe oxidation of hydrogen chloride, which comprises a support and themetal salts or metal oxides applied thereon. The metal salts or metaloxides are loaded onto the support such that the catalyst comprises:1-20 wt % of copper, 0.01-5 wt % of boron, 0.1-10 wt % of alkali metalelement, 0.1-15 wt % of one or two or more of rare earth elements, ≧0-10wt % of one or two or more of magnesium, calcium, barium, manganese,iron, nickel, cobalt, zinc, ruthenium or titanium, each based on thetotal weight of the catalyst.

The catalyst and the preparation method thereof according to theinvention will be further described in detail with reference to thefollowing Examples. But the present invention is not limited by theseExamples in any way. In the following Examples and Comparative Examples,“%” used refers to “wt %” unless specified otherwise.

The following Examples and Comparative Examples are carried out in afixed bed reactor. The general reaction procedure is as follows:hydrogen chloride and oxygen are fed into the top of a quartz tubereactor with their pressures respectively controlled by pressurestabilization valves and their flow rates respectively controlled bymass flow controllers, and the gas flows pass the catalyst bed toconduct the reaction after preheated with quartz sands. The reactionproduct is absorbed by an excess potassium iodide solution, and theamount of resultant chlorine is measured by the iodometric method andthe amount of unreacted hydrogen chloride is measured by acid-basetitration for calculating the yield of chlorine.

In addition, in the following Examples and Comparative Examples, theaqueous solution containing active ingredients is slight excess inimpregnation steps, and the solid is directly dried after impregnation,thus there is no loss of the active ingredients.

EXAMPLE 1

In a 40 ml of aqueous solution that contains 26.3 g CuCl₂.2H₂O, 60 g ofHY molecular sieve (rare earth HY molecular sieve, manufactured byMingmeiyoujie Mining Co. Ltd., Mingguang City, the same below) isimpregnated for 12 h, then dried at 90° C. for 16 h. The resultant solidis re-dispersed in a 50 ml of aqueous solution that contains 0.92 gH₃BO₃, 4.95 g KCl, 8.15 g Ce(NO₃)₃.6H₂O and 4.05 g Nd(NO₃)₃.6H₂O toperform impregnation for 12 h, then dried at 90° C. for 16 h. The driedsolid is calcined at 500° C. for 4 h to obtain 90 g of active catalyst.It is tableted to obtain catalyst granules of 30-60 mesh. 6 g of thecatalyst of 30-60 mesh is loaded in a fixed bed reactor to conduct areaction with of the flow rates of hydrogen chloride and oxygen of 100ml/min respectively, with the reaction temperature at 380° C. and thereaction pressure at 0.18 MPa. After 4 h of reaction, the chlorine yieldis 88.6%; and after 100 h of reaction, the chlorine yield is 89.0%. Theactivity of the catalyst is stable. After 1000 h of reaction, thechlorine yield is 87.8%, that is, the catalyst still keeps quite a highactivity.

COMPARATIVE EXAMPLE 1

In a 42 ml of aqueous solution that contains 26.3 g CuCl₂.2H₂O, 60 g HYmolecular sieve is impregnated for 12 h, then dried at 90° C. for 16 h.The resultant solid is re-dispersed in a 54 ml of aqueous solution thatcontains 4.95 g KCl, 8.15 g Ce(NO₃)₃.6H₂O and 4.05 g Nd(NO₃)₃.6H₂O toperform impregnation for 12 h, then dried at 90° C. for 16 h. Afterbeing calcined at 500° C. for 4 h, 90 g of active catalyst is obtained.It is tableted to obtain catalyst granules of 30-60 mesh.

With the same reaction conditions as in Example 1, the chlorine yield is88.2% after 4 h of reaction, and is 86.4% after 100 h of reaction.Obviously, the catalyst has a relatively poor stability.

It can be concluded from the comparison of Example 1 and ComparativeExample 1 that the addition of boron element improves the stability ofthe catalyst.

EXAMPLE 2

In a 41 ml of aqueous solution that contains 26.3 g CuCl₂.2H₂O, 60 gkaolin is impregnated for 12 h, then dried at 90° C. for 16 h. Theresultant solid is re-dispersed in a 49 ml of aqueous solution thatcontains 1.15 g H₃BO₃, 4.95 g KCl, 8.15 g Ce(NO₃)₃.6H₂O and 4.05 gLa(NO₃)₃.6H₂O to perform impregnation for 12 h, then dried at 90° C. for16 h. After being calcined at 500° C. for 4 h, 90 g of active catalystis obtained. It is tableted to obtain catalyst granules of 30-60 mesh.With the same reaction conditions as in Example 1, the chlorine yield is86.1% after 4 h of reaction and is 85.8% after 100 h of reaction. Theactivity of the catalyst substantially remains unchanged. After 1000 hof reaction, the catalyst still keeps its activity with the chlorineyield of 85.4%.

EXAMPLE 3

In a 45 ml of aqueous solution that contains 17.8 g CuCl₂.2H₂O and 11.5g Co(NO₃)₂.6H₂O, 60 g HY molecular sieve is impregnated for 12 h, thendried at 90° C. for 16 h. The resultant solid is re-dispersed in a 50 mlof aqueous solution that contains 0.46 g H₃BO₃, 4.95 g KCl, 8.15 gCe(NO₃)₃.6H₂O and 4.05 g Pr(NO₃)₃.6H₂O to perform impregnation for 12 h,then dried at 90° C. for 16 h. After being calcined at 500° C. for 4 h,86 g of active catalyst is obtained. It is tableted to obtain catalystgranules of 30-60 mesh. With the same reaction conditions as in Example1, the chlorine yield is 86.4% after 4 h of reaction and is 86.8% after100 h of reaction. The catalyst keeps a stable activity. The chlorineyield is 86.0% after 1000 h of reaction.

EXAMPLE 4

In a 40 ml of aqueous solution that contains 26.3 g CuCl₂.2H₂O, 60 g HYmolecular sieve is impregnated for 12 h, then dried at 90° C. for 16 h.The resultant solid is re-dispersed in a 54 ml of aqueous solution thatcontains 0.92 g H₃BO₃, 3.05 g KCl, 1.35 g Mg(NO₃)₂.2H₂O, 8.15 gCe(NO₃)₃.6H₂O and 4.05 g La(NO₃)₃.6H₂O to perform impregnation for 12 h,then dried at 90° C. for 16 h. After being calcined at 500° C. for 4 h,89 g of active catalyst is obtained. It is tableted to obtain catalystgranules of 30-60 mesh.

In a fixed bed reactor, 6 g of the catalyst prepared in Example 4 isloaded to conduct a reaction with the flow rates of hydrogen chlorideand oxygen of 150 ml/min respectively, with the reaction temperature at383° C. and the reaction pressure at 0.18 MPa. After 4 h of reaction,the chlorine yield is 85.7%, and after 100 h of reaction, is 85.2%. Theactivity of the catalyst substantially keeps activity. After 1000 h ofreaction, the chlorine yield is 85.1%.

COMPARATIVE EXAMPLE 2

In a 65 ml of aqueous solution that contains 26.3 g CuCl₂.2H₂O, 3.05 gKCl, 1.35 g Mg(NO₃)₂ 2H₂O, 8.15 g Ce(NO₃)₃.6H₂O and 4.05 gLa(NO₃)₃.6H₂O, 60 g HY molecular sieve is impregnated for 12 h, thendried at 90° C. for 16 h. After being calcined at 550° C. for 4 h, 90 gof active catalyst is obtained. It is tableted to obtain catalystgranules of 30-60 mesh. With the same hydrogen chloride oxidationreaction conditions as in Example 4, the chlorine yield is 82.9% after 4h of reaction and is 82.0% after 100 h of reaction. The chlorine yieldis 80.2% after 1000 h of reaction

It can be concluded from the comparison between Example 4 andComparative Example 2 that the catalyst obtained through the two-stepimpregnation process has a significantly higher activity than that ofthe catalyst prepared by the one-step impregnation process has. Use ofthe inventive catalyst in a reaction for production of chlorine byoxidation of hydrogen chloride can increase the chlorine yield by about3 percent.

1. A catalyst for producing chlorine by oxidation of hydrogen chloridecomprising a support and active ingredients, wherein the activeingredients comprise: 1-20 wt % of copper, 0.01-5 wt % of boron, 0.1-10wt % of alkali metal element(s), 0.1-15 wt % of one or more rare earthelements, and 0-10 wt % of one or more elements selected from the groupconsisting of: magnesium, calcium, barium, manganese, iron, nickel,cobalt, zinc, ruthenium and titanium, based on the total weight of thecatalyst. 2-14. (canceled)
 15. The catalyst according to claim 1,wherein the active ingredients comprise: 4-15 wt % of copper, 0.1-4 wt %of boron, 2-7 wt % of alkali metal element(s), 1-11 wt % of one or morerare earth elements, and 1-8 wt % of one or more elements selected fromthe group consisting of: magnesium, calcium, barium, manganese, iron,nickel, cobalt, zinc, ruthenium and titanium.
 16. The catalyst accordingto claim 15, wherein the active ingredients comprise: 5-12 wt % ofcopper, 0.15-3 wt % of boron, 2.5-6 wt % of alkali metal element(s), 2-9wt % of one or more rare earth elements, and 2-6 wt % of one or moreelements selected from the group consisting of: magnesium, calcium,barium, manganese, iron, nickel, cobalt, zinc, ruthenium and titanium.17. The catalyst according to claim 1, wherein the support comprises oneor more of: a molecular sieve, kaolin, diatomite, silica, alumina,titania or zirconia, and the support comprises 60-90 wt % of the totalweight of the catalyst.
 18. The catalyst according to claim 17, whereinthe alkali metal element is lithium, sodium, potassium or cesium. 19.The catalyst according to claim 18, wherein the rare earth elementcomprises one or more lanthanide elements.
 20. A method of making thecatalyst of claim 1, comprising: (a) preparing a solution by dissolvinga copper-containing compound and optionally a compound containing atransition metal other than copper in water, then impregnating a supportwith the solution, and drying the impregnated support; (b) dissolving aboron-containing compound, an alkali metal-containing compound, analkaline earth metal-containing compound and a rare earthmetal-containing compound in water, then impregnating the dried solidobtained in step (a) therein, and drying the impregnated solid; and (c)calcining the solid obtained in step (b) at a temperature of 450-650° C.for 1-5 h so as to obtain the catalyst.
 21. The method according toclaim 20, wherein the copper-containing compound is a soluble salt ofcopper.
 22. The method according to claim 20, wherein the compoundcontaining a transition metal other than copper is a soluble salt ofmanganese, iron, nickel, cobalt, zinc, ruthenium or titanium.
 23. Themethod according to claim 20, wherein the boron-containing compound is asoluble boron compound.
 24. The method according to claim 20, whereinthe alkali metal-containing compound is a soluble salt of lithium,sodium or potassium.
 25. The method according to claim 20, wherein thealkaline earth metal-containing compound is a soluble salt of magnesium,calcium or barium.
 26. The method according to claim 20, wherein therare earth metal-containing compound is a soluble salt of a rare earthelement.
 27. The method according to claim 20, wherein thecopper-containing compound is one or more of: cupric nitrate, cupricchloride or cupric acetate; the boron-containing compound is one or moreof: boric acid, sodium borate or potassium borate; the compoundcontaining the transition metal other than copper is one or more of:nitrates, chlorides or acetates of manganese, iron, nickel, cobalt orzinc; the alkali metal-containing compound is one or more of: achloride, a nitrate, an acetate, a carbonate or a borate of sodium orpotassium; the alkaline earth metal-containing compound is one or moreof: chlorides, nitrates, acetates, carbonates or borates of magnesium orcalcium; and the rare earth metal-containing compound is one or more of:nitrates of cerium, lanthanum, praseodymium or neodymium.
 28. The methodaccording to claim 20, wherein the active ingredients comprise: 4-15 wt% of copper, 0.1-4 wt % of boron, 2-7 wt % of alkali metal element(s),1-11 wt % of one or more rare earth elements, and 1-8 wt % of one ormore elements selected from the group consisting of: magnesium, calcium,barium, manganese, iron, nickel, cobalt, zinc, ruthenium and titanium.29. The method according to claim 28, wherein the active ingredientscomprise: 5-12 wt % of copper, 0.15-3 wt % of boron, 2.5-6 wt % ofalkali metal element(s), 2-9 wt % of one or more rare earth elements,and 2-6 wt % of one or more elements selected from the group consistingof: magnesium, calcium, barium, manganese, iron, nickel, cobalt, zinc,ruthenium and titanium.
 30. The method according to claim 20, whereinthe support comprises one or more of: a molecular sieve, kaolin,diatomite, silica, alumina, titania or zirconia, and the supportcomprises 60-90 wt % of the total weight of the catalyst.